Preparation of organic compounds of metals



United t s Patent 9 7,

Ser. No.

The present application is a continuation-in-part of my u copending application Ser. No. 811,262 filed May 6, 1959 now matured into U.S. Patent 3,007,858, the disclosure of which is incorporated herein by reference as fully as if it had been set forth in its entirety.

This invention relates to the preparation 'of'organic compounds of metals and more particularly to a new and improved process for making such compounds.

In my said copending application there is broadly disclosed a process for the preparation of organo metallic compounds. However, the claims of said application are limited to the preparation of alkyl lead compounds. The purpose of the present application is to cover the process in its broader aspects and also to cover specific processes other than the manufacture of alkyl-leadcompounds.

One of the objects of the invention is to cover broadly a process for making organic compoundsof metals by electrolyzing a sacrificial anode in an electrolyte in which said anode dissolves, said electrolyte containing as an essential component an organic compound of a metal which is capable of liberating free organic radicals during the electrolyzing action, and adding an extraneous organic halide to said electrolyte.

Another object of the invention is to provide a process of the type described for making organo lead compounds in which aromatic radicals are linked to metallic lead.

A further object of the invention is to.provide a process of the type described for making organic compounds of metals other than lead.

A more specific object of the invention is to provide a process of the type described for making organic compounds of aluminum. Other objects will appear hereinafter.

sacrificial anodeprocesses are described in the literature. Thus, Kondyrew, Berichte der Deutsche Chemische' electrolyzed in a solution of a Grignard-reagent with the addition of an extraneous organic halide.

In accordance with the present invention organic compounds of metals dissolved in an organic solvent are electrolyzed using a sacrificial anode and adding an extraneous organic halide to the electrolyte. The organic compounds of the metals in the electrolyte-are preferably Grignard reagents, that is, compounds having the formula RMgX where R represents anorganic radical, Mg represents magnesium, and .X represents a halogen atom, for

example, chlorine, bromine or iodine. When a .Grignard reagent is employed as the electrolyte, as the electrolyzing procedure proceeds, magnesium normally tends to form at the cathode and this can cause serious problems, such as bridging between the anode and the cathode, but the 3,391,066 Patented July 2, 1 968 extraneous organic halide reacts with this magnesium and reconverts it to arGrignard reagent, thereby avoiding the deposit of the magnesium at the cathode. While the theory of the reaction is not clearly understood it is believed that free radicals are formed corresponding to the organic radicals of the Grignard reagent and these react with the metal which is electrolyzed at the anode. The extraneous organic halide also takes part in this reaction and the organic-radicals thereof eventually also combine with the metal of the sacrificial anode, perhaps after first forming a Grignard reagent or possibly in a direct manner due to the nascent state ofthe metal.

The term' organic halide as used herein is intended .to include organic chlorides, bromides and iodides. By the term extraneous organic halide is meant an organic halide which is added as such as distinguished from the organic halide used initially to form a Grignard reagent from magnesium. In terms of the magnesium present in the electrolyte, the-extraneous organic halide is that organic halide which is present in a quantity in excess of one mole of RX per mole of magnesium, where RX has the previously described significance. The organo metallic compounds whichare formed by the reaction of the organic radicals in the electrolyte with the metal of the anode can be separated from the electrolyte in any suitable manner.

The cathode may be composed of a suitable conducting but non-reactive material, such as platinum, stainless steel, ordinary steel, graphite, or other conducting material which does not dissolve in the electrolyte. In some cases the cathode may be composed of the same material as the anode. Thus, both the cathode and the anode can be composed of lead. It is preferable, however, that the anode be composed of lead and the cathode of steel.

The solvent for the Grignard reagent must be relatively inert under the conditions of the process. For this purpose it should not contain any labile hydrogen which is readily reactive. It may have some dielectric properties but -it should have sufiicient conductivity to permit the passage :of a current between the anode and the cathode. Solvents the dibutylether of diethylene glycol and the dimethylether of dipropylene glycol. Example-s of solvents containing nitrogen are trihexylamine, triamylamine, pyridine and quinoline.

The temperatures used are normally above the freezing point of the solution and below the boiling points of the solvent and the desired organic metal compound. In general, it is preferable to use temperatures within the range of 20 C. to C.

The pressures used are normally sutficient to maintain the liquid phase with the particular solvent and temperature conditions employed. It is usually preferably'to operate the process under a superatmospheric pressure which does not exceed five atmospheres.

I The process can be carried out using a single extraneous organic halide with a single Grignard reagent in which the organic radicals of the Grignard reagent and the organic halide are the same. In this way the resultant organo Ill metallic compounds contain only one type or organic radical linked to a metallic atom corresponding to the metal of the sacrificial anode. The reaction can also be carried out with two or more extraneous organic halides introduced into an electrolyte containing a single Grignard reagent in which at least one of the orgamc radicals or" the Grignard reagent and the organic halides is different from another. In this way organo metallic compounds are obtained in which two or more difierent types of organic radicals are linked to a metal corresponding to the metal of the sacrificial anode. Similarly, the electrolyte can be composed of mixtures of Grignard reagents. To illustrate more specifically, the electrolyte can be composed of methyl magnesium chloride and the extraneous organic chloride can be phenyl chloride, cyclohexyl chloride, benzyl chloride, or the like. In this way compounds are obtained in which methyl radicals and another organic radical corresponding to that of the organic halide are linked to the metal of the sacrificial anode. Alternatively, the Grignard reagent can be phenyl magnesium chloride and phenyl chloride is added as the extraneous organic halide whereby organo metallic compounds are obtained in which only phenyl radicals are linked to the metal of the sacrificial anode. Instead of the chlorides the corresponding iodides or bromides may be used in the Grignard reagent and/or the organic halide. A mixture or an alkyi halide and an aromatic halide may be used as the extraneous organic halide. For example, a mixture of methyl chloride and phenyl chloride can be added to a methyl- Grignard reagent, or a mixture of ethyl chloride and phenyl chloride can be added to a methyl-Grignard reagent, or a mixture of ethyl chloride and phenyl chloride can be added to an ethyl Grignard reagent.

The invention is especially valuable in making orgamc lead compounds, that is to say, lead is used as the sacrilicial anode. However, the invention is applicable to other metals which are capable of being electrolyzed in a Grignard reagent. Examples of such other metals are aluminum, calcium, zinc, cadmium, manganese. mercury, lanthanum, thallium, arsenic, bismuth, tellurium and selenium. By employing such metals as the sacrificial anode it is possible to form products in which organic radicals of the Grignard reagent and/or the extraneous organic halide, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, pnenyl, benzyl, and the like, are linked directly to the metal of the sacrificial anode.

The quantity of the solvent employed for the Grignard reagent should preferably be such that the electrolyte remains in liquid phase during the reaction and for this purpose it is desirable to employ a minimum or" about one mole of an organic ether solvent, for example, the dibutylether or diethylene glycol, or the hexylethylether of diethylene glycol per mole of Grignard reagent. The

maximum amount of such organic ether solvent employed initially will ordinarily not exceed two moles of such solvent per mole of Grignard reagent.

Especially good results have been obtained by dissolving the Grignard reagent in a mixture of solvents at least one of which is an organic ether solvent or the type previously described and another is an aromatic hydrocarbon solvent such as benzene, toluene or xylene, but preferably benzene. The addition of tetrahydrofuran is desirable because it increases the conductivity initially and shortens the run. Where tetrahydrofuran is employed it is preferable to use about 0.5 to 1.5 moles per mole of total Grignard reagent. Where an aromatic hydrocarbon such as benzene is employed it is preferable to use about 3 to 7.5 moles of such aromatic hydrocarbon per mole of Grignard reagent. Where both tetrahydrofuran and an aromatic hydrocarbon such as benzene are employed it is preferable to use an amount within a weight ratio of tetrahydrofuran to aroma ic hydrocarbon of 1:4 o 1:?-

in carrying out the process the initial Grignard concentration is subject to Wide variation but is preferably Wlthln the range of 0.5 to 2.5 millimoles of Grignard per gram of solution.

The quantity of the extraneous organic halide is prefer- .lbly within the range of 0.1 to 1.5 moles per mole of tirignard.

The invention has been operated over a wide range of current densities and at varying voltages. The spacing and size or the electrodes and the type of electrode will determine the current density. In general, a minimum current density of around 0.01 ampere per square centimeter is used. Direct current voltages as low as 2% to 3 volts have been used and the process can also be carried out with voltages of 100 to 300 volts but in general it is desirtble to use direct current voltages around 2 to 35 volts.

lDne way of carrying out the process is to electrolyze the electrolyte until the Grignard reagent therein is sub- .ttantially exhausted. Another way is to separate a part of the electrolyte and recover at least a part of the desired product. thereafter returning separated solvent and also llGrignard reagent to the cell.

in carrying out the process it is sometimes desirable to control the magnesium halide content by removing magnesium halide from the electrolyte. This can be accomplished by using as one of the solvents an organic ether which will form an etherate with the magnesium halide or by adding dioxane which also forms a complex insoluble substance with the magnesium halide, or by adding another material such as pyridine which forms .t complex insoluble substance. The insoluble complexes containing the magnesium halide can then be removed lIll'Dm the electrolyzed solution either before or after separation of the organo metallic compound by filtration or other suitable means, and the residual solution is returned tor re-use 111 the electrolyzing cell. Where the necessity for this separate step arises the molar ratio of the magnesium halide to Grignard reagent is preferably controlled to that it does not exceed 2:1. However, the necessity does not ordinarily arise in a solvent system containing .t sutficiently large amount of an aromatic hydrocarbon, ltllCh as benzene, to maintain all of the components of the system in solution and reduce the viscosity.

The current requirements are normally within the range of 2 amperes to amperes. The current density will trsually vary within the range of 2 amperes per square foot to 30 amperes per square foot. The optimum current tzlensity will vary somewhat depending on the temperature. in general, the higher the temperature used, the higher the current density. The temperatures of 20 C., 25 C., i0" C., C., C., C., and C. can be used with satisfactory results.

lit is preferable to operate with a total concentration of extraneous organic halides within the range of 0.1 to 1.5 moles per mole of total Grignard reagent. The reaction can be controlled by varying the respective concentrations at two or more organic halides used in carrying out the itrocess. The optimum concentrations will also vary depending upon the product which is being made. Thus, in making tetramethyl lead using methyl magnesium chloride with extraneous methyl chloride, the optimum conttentration of methyl chloride is within the range of 0.1 to 0.7 mole per mole of methyl magnesium chloride. On the other hand, in making tetraethyl lead from ethyl magnesium chloride with extraneous ethyl chloride, the optimum concentration of extraneous ethyl chloride is within the range of 0.7 to 1.1 mole per mole of total tirignard reagent. This optimum concentration is preferably chosen at a level which minimizes the formation at by-product gases caused by the combination of lib trated hydrocarbon radicals with each other.

The invention will be further illustrated but is not limted by the following examples in which the quantities are stated in parts by weight unless otherwise indicated.

Example I The process can be carried out in various types of cells but one cell which has been found to be particularly suitable is a pipe cell made from a 2 inch diameter steel pipe about 30 inches long with /2 inch flange openings welded on opposite sides of the pipe 24 inches apart to form inlet and outlet openings for introducing and withdrawing the electrolyte. The center of the bottom inlet opening is about 2 inches from the bottom of the cell and the center of the top outlet opening is about 4 inches from the top of 'the cell. A layer of fine mesh woven polypropylene filaments is used as a liner on the inside of the pipe to separate the cathode from lead pellets which form the anode material. A lead rod is inserted into the center of the cell longitudinally and connected to a positive source of electricity. A negative source of electricity is connected to the outside of the pipe so that the pipe itself forms the cathode. The area of the cathode is approximately 92 square inches. The area of the screening is approximately 84.25 square inches. The available volume within the cell is approximately 18.65 cubic inches. The cell is charged with lead pellets. g

The apparatus is equipped with a recirculating system including a pump whereby the electrolyte can be pumped externally of the cell through a heat exchanger in order to control the temperature. The temperature can also be controlled by providing a cooling jacket around the cell.

A methyl-Grignard solution is prepared by reacting methyl chloride and metallic magnesium in the dibutylether of diethylene glycol in proportions of approximately one mole of methyl chloride per mole of metallic magnesium per mole of said ether. The solution is recirculated externally of the cell through a heat exchanger at an average flow rate of 4 gallons per minute until a temperature of 38 C. is obtained. Extraneous phenyl chloride is added to the cell in amount sufficient to give an initial concentration of 0.5 mole per mole of Grignard reagent. The current is turned on using a direct current voltage of 30 volts and an amperage of amperes. The run is carried out for 10 hours. The product is a mixture of organic lead compounds containing methyl and phenyl radicals linked to metallic lead.

Example I1 4 The procedure is the same as in Example I except that one mole of tetrahydrofuran per mole of Grignard reagent is added to the electrolyte initially.

Example H1 The procedure is the same as in Example I except that 4.5 moles of benzene per mole of Grignard reagent is added to the electrolyte initially.

Example IV The procedure is the same as in Example I except that one moleof tetrahydrofuran per mole of Grignard reagent and 4.5 moles of benzene per mole of Grignard reagent are added to the electrolyte initially.

Example V The procedure is the same as in Example I except that 0.3 mole of methyl chloride per mole of Grignard reagent and 0.5 mole of phenyl chloride per mole of Grignard reagent are maintained in the electrolyte.

Example VI Example VII The procedure is the same as in Example HI except that 0.3 mole of methyl chloride per mole of Grignard reagent and 0.6 mole of phenyl chloride per mole of Grignard reagent are maintained in the electroylte.

6 Example VHI The procedure is the same as in Example IV except that 0.3 mole of methyl chloride per mole of Grignard reagent and 0.6 mole of phenyl chloride per mole of Grignard reagent'are maintained in the electrolyte.

Example IX In this example a different type of cell is used. The cell consists of a closed vessel having a valved inlet for introducing the extraneous organic halide and a valved outlet for the release of gases which is normally closed and is equipped with a pressure gauge to indicate the amount of pressure which is built up within the cell. The electrodes consist of seven 4-inch by 2-inch aluminum plates. These plates are held suspended from the top of the cell by means of an insulated support. They are separated from each other by a distance of about A; inch. The insulated support used for supporting the plates is made of polytetrafiuoroethylene (Teflon). Plates 1, 3, 5 and 7 are connected to the negative lead of a direct current power source While places 2, 4 and 6 constituting the anode are connected to the positive lead from the same power source.

A suificient amount of electrolyte is placed in the cell to cover the electrodes up to 3 inches from the bottom of the plates, thus giving an anode working surface of 0.25 square feet.

The electrolyte consists of 620 ml. of hexylmagnesium bromide (C H MgBr), and ml. of hexylbromide (C H Br). The solvent used is the hexylethylether of diethylene glycol, that is, a diether of ethylene glycol in which one of the terminal ether groups is a hexylether group and the other terminal ether group is an ethylether group. A sutficient amount of solvent is used to give :a concentration of hexylmagnesium bromide before the addition of hexylbromide of 1.36 millimoles per gram. After the addition of the hexylbromide the concentration of the hexylmagnesium bromide in the solution is 1.13 millimoles per gram. A total of 0.837 mole of hexylmagnesium bromide is therefore introduced into the cell.

The process is carried out until 15.16 ampere hours of electricity have been used employing a direct current voltage of 265-27 volts thoughout the run. The temperature is kept at 35 C. to 45 C. The average current density during the run is 5.95 ampere hours. The current eflicienc is 134.2%.

Aluminum dissolves from the anodes and forms trihexyl aluminum. The solution produced by the electrolyzing process is transferred from the cell to a separatory funnel where it separates into two layers. Trihexyl aluminum is found in both layers.

The average pressure developed in the cell throughout the run is 3 p.s.i.g. The solution is agitated throughout the run by means of a magnetic stirrer which is disposed in the bottom of the cell directly beneath the electrodes. There is no appreciable gas formation during the process.

Example X The procedure is the same as in Example IX except that instead of using aluminum electrodes. 3 stainless steel plates 2-inch by 4-inch in size are employed as the cathode and 2 lead plates 2-inch by 4-inch in size are employed as the anode. The plates are set Ms inch apart.-The working surface is 0.159 square feet.

The electrolyte consists of 600 ml. of phenyl magnesium bromide solution and 100 ml. of phenyl bromide. The phenyl'magnesiu-m bromide solution is prepared by reacting 550 grams of phenyl bromide with grams of magnesium in 1725 ml. of the hexylethylether of diethylene glycol.

The solution is agitated by means of a magnetic stirrer as described in Example IX. A direct current voltage of 25.6-26.8 volts is applied until 13.46 ampere hours of current has been used. The temperature is maintained at 55 C. The average pressure is around 3 p.s.i.g.

Tetraphenyl lead is recovered from the electrolyte. No appreciable gas is formed.

Example XI The procedure is the same as described in Example lX except that zinc electrodes are substituted for the aluminum electrodes. The products contain hexyl radicals linked to metallic zinc.

Example XII The procedure is the same as in Example IX except that manganese electrodes are substituted for :he llumlnum electrodes. The products contain hexyl radicals linked to metallic manganese.

Example XIII The procedure is the same as in Example [X :xcept that cadmium electrodes are substituted for the aluminum electrodes. The products contain hexyl radicals linked to metallic cadmium.

Example XIV The procedure is the same as in Example lX except that bismuth electrodes are substituted for the aluminum electrodes. The products contain hexyl radicals .inked to metallic bismuth.

Example XV The procedure is the same as in Example K except that aluminum electrodes are substituted for he :ead electrodes. The product contains phenyl radicals linked to metallic aluminum.

In a like manner, Example IX can be carried out using methyl chloride, ethyl chloride, propyl chloride. :sopropyl chloride, butyl chloride, lsobutyl chloride. secondary butyl chloride, tertiary butyl chloride. and/or the corresponding bromides or iodides instead pt the hexyl bromide. Methyl magnesium chloride. ethyl magnesium chloride. propyl magnesium chloride. isopropyl magnesium chloride. butyl magnesium chloride, amyl magnesium chloride. hexyl magnesium chloride. and the like can also be substituted for the hexyl magnesium bromide in Example IX. Likewise two or more different organic halides can be employed in Example [X and can be added to the cell either initially or sequentially. For example. :0 a Grignard reagent containing methyl magnesium chloride there 15 added 0.3 mole per mole of methyl magnesium chloride of methyl chloride and 0.6 mole per mole of methvl magnesium chloride of hexyl chloride. instead of the hexyl chloride tertiary butyl chloride can be used or tertiary butyl bromide can be employed. The products contam hydrocarbon radicals linked to metallic aluminum. in a similar manner the organic halides specifically set forth above are used in Examples XI, XII. XIII and .(IV to produce organo metallic compounds of zinc. manganese. cadmium and bismuth. respectively, having hydrocarbon radicals linked directly to the metal.

It will be recognized that various methods including fractional distillation. vacuum distillation and steam distillation may be employed in recovering the products. The present invention is not concerned with the particular manner in which the products are recovered.

The invention is hereby claimed as follows:

1. A process for preparing organo metallic compounds which comprises electrolyzing, using a sacrificial metal anode, a substantially anhydrous solution or a Grignard reagent in a substantially inert organic solvent for said Grignard reagent, adding extraneous organic halide to said solution, and recovering from the resultant product an organo metallic compound consisting of hydrocarbon radicals linked directly to the metal of he sacrificial anode.

2. A process for preparing organo metallic compounds which comprises electrolyzing, using a sacrificial :netal anode, a substantially anhydrous solution or .1 tirignard reagent in a substantially inert organic solvent :or laid Grignard reagent, adding to said solution 0.1 to l.:' moles lllll66 t ll til it it A process for preparing organo metallic compounds which comprises electrolyzing, using a sacrificial metal .ttode. a substantially anhydrous solution of a Grignard agent in a substantially inert organic solvent for said ollgnard reagent. adding to said solution a plurality of uttraneous organic halides in a total amount correspond- .llg to 0.1 to l.5 moles per mole of Grignard reagent, and covering from the resultant product an organo metallic mpound consisting of hydrocarbon radicals linked :nrectly to the metal of the sacrificial anode.

ll. A process for preparing phenyl lead compounds which comprises electrolyzing, using a lead anode, a subttantially anhydrous solution of a Grignard reagent in a .tlustantiallv inert organic solvent for said Grignard relgent, employing an electrolyzing current effective to .ltluse said anode to dissolve in said solution of said .lrignard reagent in said organic solvent, adding extranellLlS phenyl halide to said solution, and recovering from the resultant product an organic lead compound consistmg of phenyl radicals linked directly to metallic lead.

wl. process for preparing organic lead compounds tmlCh comprises electrolyzing, using a lead anode, a subrtantially anhydrous solution of an alkyl Grignard re- ;tgent in 1 substantially inert organic solvent for said Grignard reagent, employing an electrolyzing current .ttiective to cause said lead anode to dissolve in said solution of said Grignard reagent in said organic solvent, .tdding a plurality of extraneous organic halides to said itDllltlOl'l including an alkyl chloride and a phenyl chloride, and recovering from the resultant product organic lead .tompounds consisting of both alkyl radicals and phenyl dicals linked directly to metallic lead.

ti. A process for reparing organic aluminum compounds which comprises electrolyzing, using an aluminum anode. a substantially anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said tirignard reagent employing an electrolyzing current effective to cause said aluminum anode to dissolve in lard solution of said Grignard reagent in said organic solvent. adding extraneous hydrocarbon halide to said .olution. and recovering from the resultant product an organic aluminum compound consisting of hydrocarbon radicals linked directly to metallic aluminum.

l. A process for preparing organic aluminum compounds which comprises electrolyzing, using an alu- .ninum anode. a substantially anhydrous solution of a tirignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing current erfective to cause said aluminum anode to dis- .ulve in said solution of said Grignard reagent in said iuganic solvent, adding to said solution a plurality of txtraneous hydrocarbon halides in which the hydrocarbon radicals are different from each other, and re- .aovering from the resultant product organic aluminum compounds consisting of hydrocarbon radicals linked dirctly to metallic aluminum.

it. A process for preparing organic zinc compounds which comprises electrolyzing, using a zinc anode, a sublubstantially anhydrous solution of a Grignard reagent in .l substantially inert organic solvent for said Grignard .tgent employing an electrolyzing current effective to sense said .ZlHC anode to dissolve in said solution of said tirignard reagent in said organic solvent, adding extrane- .llllS hydrocarbon halide to said solution, and recovertllllg from the resultant product an organic zinc compound consisting or hydrocarbon radicals linked directly to :uetallic zinc.

A process for preparing organic zinc compounds which comprises electrolyzing, using a zinc anode, a tubstantiallv anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing current effective to cause said zinc anode to dissolve in said solution of said Grignard reagent in said organic solvent, adding to said solution a plurality of extraneous hydrocarbon halides in which the hydrocarbon radical are different from each other, and recovering from the resultant product organic zinc compounds consisting of hydrocarbon radicals linked directly to metallic zinc.

10. A process for preparing organic manganese compounds which comprises electrolyzing, using a manganese anode, a substantially anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing current effective to cause said manganese anode to dissolve in said solution of said Grignard reagent in said organic solvent, adding extraneous hydrocarbon halide to said solution, and recovering from the resultant product an organic manganese compound consisting of hydrocarbon radicals linked directly to metallic manganese.

11. A process for preparing organic manganese compounds which comprises electrolyzing, using a manganese anode, a substantially anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing current effective to cause said manganese anode to dissolve in said solution of said Grignard reagent in said organic solvent, adding to said solution a plurality of extraneous hydrocarbon halides in which the hydrocarbon radicals are different from each other, and recovering from the resultant product organic manganese compounds consisting of hydrocarbon radicals linked directly to metallic manganese.

12. A process for preparing organic cadmium compounds which comprises electrolyzing, using a cadmium anode, a substantially anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing current effective to cause said cadmium anode to dissolve in said solution of said Grignard reagent in said organic solvent, adding extraneous hydrocarbon halide to said solution, and recovering from the resultant product an organic cadmium compound consisting of hydrocarbon radicals linked directly to metallic cadmium.

13. A process for preparing organic cadmium compounds which comprises electrolyzing, using a cadmium anode, a substantially anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing current effective to cause said cadmium anode to dissolve in said solution of said Grignard reagent in said organic solvent, adding to said solution a plurality of extraneous hyrocarbon halides in which the hydrocarbon radicals are different from each other, and recovering from the resultant product organic cadmium compounds consisting of hydrocarbon radicals linked directly to metallic cadmium.

14. A process of preparing organic bismuth compounds which comprises electrolyzing, using a bismuth anode, a substantially anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing cur-rent effective to cause said bismuth anode to dissolve in said solution of said Grignard reagent in said organic solvent, adding extraneous hydrocarbon halide to said solution, and recovering from the resultant product an organic bismuth compound consisting of hydrocarbon radicals linked directly to metallic bismuth.

15. A process for preparing organic bismuth compounds which comprises electrolyzing, using a bismuth anode, a substantially anhydrous solution of a Grignard reagent in a substantially inert organic solvent for said Grignard reagent employing an electrolyzing current effective to cause said bismuth anode to dissolve in said solution of said Grignard reagent in said organic solvent, adding to said solution a plurality of extraneous hydrocarbon halides in which the hydrocarbon radicals are different from each other, and recovering from the resultant product organic bismuth compounds consisting of hydrocarbon radicals linked directly to metallic bismuth.

16. An electrolyte for making organo metallic com pounds comprising a substantially anhydrous solution of at least one Grignard reagent in a substantially inert sol vent for said Grignard reagent and at least one extraneous organic halide, the total concentration of extraneous organic halide being within the range of 0.1 to 1.5 moles per mole of Grignard reagent.

17. An electrolyte for making organo metallic compounds comprising a substantially anhydrous solution of at least one Grignard reagent in a substantially inert solvent for said Grignard reagent and at least one extraneous organic halide, the total concentration of extraneous organic halide being within the range of 0.1 to 1.5 moles per mole of Grignard reagent, and the concentration of Grignard reagent being within the range of 0.5 to 2.5 miliimoles of Grignard reagent per gram of solution.

18. An electrolyte for making organo metallic compounds comprising a substantially anhydrous solution of at least one Grignard reagent in a substantially inert solvent for said Grignard reagent and at least one extraneous organic halide, the total concentration of extraneous organic halide being within the range of 0.1 to 1.5 moles per mole of Grignard reagent, the concentration of Grignard reagent being within the range of 0.5 to 2.5 millirnoles of Grignard reagent per gram of solution, said solvent containing at least one mole per mole of total Grignard reagent of a dialkylether of a polyoxyalkylene glycol containing 2 to 4 oxygen atoms in the glycol, 2 to 4 carbon atoms in the alkylene groups of the glycol, and 2 to 8 carbon atoms in the alkyl groups of the ether radicals, up to 1.5 moles of tetrahydrofur-an per mole of total Grignard reagent and up to 7.5 moles of benzene per mole of total Grignard reagent.

References Cited UNITED STATES PATENTS 2,535,193 12/1950 Calingaert et al 260-437 3,007,857 11/1961 Braithwaite 204-59 3,007,858 11/1961 Br-aithwaite 20459 FOREIGN PATENTS 839,172 6/ 1960 Great Britain.

OTHER REFERENCES Journal of American Chemical Society, French, et al. vol. 52 (1930) pp. 4904-4906.

HOWARD S. WILLIAMS, Primary Examiner.

JOHN R. SPECK, JOHN H. MACK, WINSTON A.

DOUGLAS, Examiners.

B. JOHNSON, Assistant Examiner. 

1. A PROCESS FOR PREPARING ORGANO METALLIC COMPOUNDS WHICH COMPRISES ELECTROLYZING, USING A SACRIFICIAL METAL ANODE, A SUBSTANTIALLY ANHYDROUS SOLUTION OF A GRIGNARD REAGENT IN A SUBSTANTIALLY INERT ORGANIC SOLVENT FOR SAID GRIGNARD REAGENT, ADDING EXTRANEOUS ORGANIC HALIDE TO SAID SOLUTION, AND RECOVERING FROM THE RESULTANT PRODUCT AN ORGANO METALLIC COMPOUND CONSISTING OF HYDROCARBON RADICALS LINKED LINKED DIRECTLY TO THE METAL OF THE SACRIFICIAL ANODE. 